CN109014241B - Method for preparing silver micron hollow frame structure material - Google Patents
Method for preparing silver micron hollow frame structure material Download PDFInfo
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- CN109014241B CN109014241B CN201810995204.1A CN201810995204A CN109014241B CN 109014241 B CN109014241 B CN 109014241B CN 201810995204 A CN201810995204 A CN 201810995204A CN 109014241 B CN109014241 B CN 109014241B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
The invention discloses a method for preparing a silver micron hollow frame structure material. The invention is obtained by the following steps: firstly, AgNO with a certain concentration is prepared at room temperature3An aqueous solution; then, to AgNO3Adding proper amount of structure directing agent HF and reducing agent FeSO into water solution4Forming a mixed solution; and then standing the mixed solution in a water bath at a certain temperature, keeping the mixed solution for a period of reaction time, and centrifuging, washing and drying the obtained product to obtain the silver micron hollow frame structure material. The invention provides a simple method for preparing a silver micron hollow frame structure material, and realizes large-scale production of the silver micron hollow frame structure material.
Description
Technical Field
The invention relates to the field of preparation of metallic silver materials, in particular to a method for preparing a silver alloy by using FeSO (FeSO) and taking HF as a structure directing agent4Reducing AgNO3The method of (3) is used for obtaining the silver micron hollow frame structure material. .
Background
The micro-nano silver has wide application fields. It is an important conductive medium of high-performance conductive paint, is a basic material of a flexible circuit board, a contact switch, a membrane switch and the like, and is also a material of various high-end electrodes and electromagnetic compatibility.
The application performance of the micro-nano silver is closely related to the shape and structure of the micro-nano silver, so that the preparation of micro-nano silver with different shapes and structures becomes a hot point of research in recent years. Liuchun Yan et al (CN 100531975C)The chemical reduction method under acidic condition, using water as dispersion medium, using glucose or ascorbic acid reducing agent to directly reduce silver nitrate in the solution, using nitric acid or glacial acetic acid as morphology regulator to prepare the flaky micron silver. Wangwei et al (CN 103170643B) use polymer microstructure optical fiber as template, spread porous cellulose acetate membrane in it, then use reducing agent stannous chloride solution to wash the internal pore of microstructure optical fiber, mix the mixed solution of glucose solution and absolute ethyl alcohol with certain concentration of silver ammonia solution in certain proportion after ice bath, press into the above microstructure optical fiber under high pressure, and then dissolve and remove polymer microstructure optical fiber and cellulose acetate with solvent respectively after reaction, obtain micron silver tubes arranged in order. Chafer et al (CN 101811196B) disclose a method for preparing dendritic micron silver powder, which comprises adding crystal form regulator phosphate into silver nitrate water solution, stirring to obtain reaction solution A; adding a reducing agent into water to obtain a reducing solution B; and quickly adding the reaction solution A into the reduction solution B for reduction reaction at room temperature under the stirring condition to obtain the dendritic micron silver. Plum, et al (CN 103506631B) disclose a method for preparing small-sized nano silver using chitosan as a reducing agent, comprising dissolving chitosan in an acetic acid solution overnight to obtain a chitosan solution; adding the newly configured chitosan solution into a flask; under stirring, the newly prepared AgNO is added3Dropwise adding the solution into the flask; and then dropwise adding a sodium citrate solution into the flask, and reacting to obtain the nano-silver sol. Cai et al (Rare Metals, 29(4): 407-4As a reducing agent, AgNO3Silver source and citric acid or sulfuric acid as structure directing agent to prepare various silver micron structure materials in spherical, flower, triangular and other shapes.
Therefore, the micro-nano silver with various shapes and structures can be prepared by adopting the prior art; however, in the prior art, the preparation method for silver micron hollow frame structure materials is still lacking.
Disclosure of Invention
The invention aims to: the method for preparing the silver micron hollow frame structure material is provided, and the large-scale production of the silver micron hollow frame structure material is realized.
The technical solution of the invention is as follows: using HF as structure directing agent and FeSO4Reducing AgNO3The method of (3) is used for obtaining the silver micron hollow frame structure material.
The method for preparing the silver micron hollow frame structure material comprises the following specific steps:
(1) preparing AgNO with a certain concentration at room temperature3An aqueous solution; according to preset HF and FeSO4And AgNO3To AgNO3Adding HF and FeSO into the aqueous solution4Stirring at 200 rpm to obtain clear mixed solution;
(2) and standing the mixed solution in a water bath at a certain temperature, keeping the mixed solution for a period of reaction time, and centrifuging, washing and drying the obtained product to obtain the silver micron hollow frame structure material.
Wherein: in the step (1), the AgNO3The concentration of the aqueous solution is 0.002-0.01 mol/L.
Wherein: in the step (1), the preset HF and FeSO4
And AgNO3The molar ratio of (5-25) to (1.1: 1).
Wherein: in the step (2), the temperature of the water bath is 35-65 ℃.
Wherein: in the step (2), the reaction time is 0.5-1 h.
The principle of the invention is as follows: AgNO3As a source of Ag, FeSO4As a reducing agent; FeSO at room temperature4The reducing power is weak and HF is added to AgNO3After in solution, F-Will be mixed with Ag+Coordination complexation, which makes the reduction rate of silver ions extremely slow at room temperature; after the reaction solution is placed in a higher temperature water bath, FeSO4The reduction capability is obviously enhanced, and F can be reduced-And Ag+The formed coordination complex ions are reduced into initial silver crystal nuclei; the silver crystal nucleus has higher surface energy, in order to reduce the surface energy of the silver crystal nucleus, the silver crystal nucleus spontaneously gathers together to form dendritic nano silver, and then the dendritic nano silver is assembled in a two-dimensional direction,forming the silver micron hollow frame structure material.
The invention has the advantages that: the large-scale production of the silver micron hollow frame structure material can be realized by a simple synthesis method. Due to the existence of the structure directing agent HF, the rate of assembling the dendritic nano silver into the traditional silver solid sheet structure is reduced, and the transition state silver micron hollow frame structure material is obtained.
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FIG. 1 is a scanning electron microscope image of a silver micron hollow frame structure material.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to examples, but it should not be construed as being limited thereto.
Example 1: preparing silver micron hollow frame structure material according to the following steps
(1) Preparing AgNO with concentration of 0.002 mol/L at room temperature3An aqueous solution; according to preset HF and FeSO4And AgNO3In a molar ratio of 5:1.1:1 to AgNO3Adding HF and FeSO into the aqueous solution4Stirring at 200 rpm to obtain clear mixed solution;
(2) and standing the mixed solution in a water bath at the temperature of 35 ℃, keeping the reaction time for 1 h, and centrifuging, washing and drying the obtained product to obtain the silver micron hollow frame structure material.
Example 2: preparing silver micron hollow frame structure material according to the following steps
(1) Preparing AgNO with concentration of 0.006 mol/L at room temperature3An aqueous solution; according to preset HF and FeSO4And AgNO3In a molar ratio of 15:1.1:1 to AgNO3Adding HF and FeSO into the aqueous solution4Stirring at 200 rpm to obtain clear mixed solution;
(2) and standing the mixed solution in a water bath at the temperature of 50 ℃, keeping the reaction time for 0.75h, and centrifuging, washing and drying the obtained product to obtain the silver micron hollow frame structure material.
Example 3: preparing silver micron hollow frame structure material according to the following steps
(1) Preparing AgNO with concentration of 0.01 mol/L at room temperature3An aqueous solution; according to preset HF and FeSO4And AgNO3In a molar ratio of 25:1.1:1 to AgNO3Adding HF and FeSO into the aqueous solution4Stirring at 200 rpm to obtain clear mixed solution;
(2) and standing the mixed solution in a water bath at the temperature of 65 ℃, keeping the reaction time for 0.5h, and centrifuging, washing and drying the obtained product to obtain the silver micron hollow frame structure material.
The scanning electron microscope pictures of the silver micron hollow frame structure materials obtained in examples 1-3 are shown in FIG. 1.
Claims (3)
1. A process for preparing the hollow silver micron-class frame structure material features use of HF as structure guiding agent and FeSO4Reducing AgNO3The method obtains the silver micron hollow frame structure material; the method is characterized by comprising the following specific steps:
(1) preparing AgNO with a certain concentration at room temperature3An aqueous solution; according to preset HF and FeSO4And AgNO3To AgNO3Adding HF and FeSO into the aqueous solution4Stirring at 200 rpm to obtain clear mixed solution;
(2) standing the mixed solution in a water bath at a certain temperature, keeping the mixed solution for a period of reaction time, and centrifuging, washing and drying the obtained product to obtain a silver micron hollow frame structure material;
in the step (1), the AgNO3The concentration of the aqueous solution is 0.002-0.01 mol/L;
in the step (1), the preset HF and FeSO4And AgNO3The molar ratio of (5-25) to (1.1: 1).
2. The method for preparing the silver micron hollow frame structure material according to claim 1, wherein the method comprises the following steps: in the step (2), the temperature of the water bath is 35-65 ℃.
3. The method for preparing the silver micron hollow frame structure material according to claim 1, wherein the method comprises the following steps: in the step (2), the reaction time is 0.5-1 h.
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| CN201810995204.1A CN109014241B (en) | 2018-08-29 | 2018-08-29 | Method for preparing silver micron hollow frame structure material |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115475952B (en) * | 2022-09-09 | 2024-01-26 | 淮阴师范学院 | Preparation method of silver nanoribbon |
| CN115488347B (en) * | 2022-09-09 | 2024-01-26 | 淮阴师范学院 | Preparation method of multilayer silver nano-sheet |
| CN115475954B (en) * | 2022-09-09 | 2024-01-26 | 淮阴师范学院 | Preparation method of hexagonal silver nano-sheet with thickened frame |
| CN115475953B (en) * | 2022-09-09 | 2024-01-26 | 淮阴师范学院 | Preparation method of netlike nano silver |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583331A (en) * | 2004-06-10 | 2005-02-23 | 复旦大学 | Preparing method for medium hole noble metal hollow microscapsule |
| CN103231069A (en) * | 2013-03-22 | 2013-08-07 | 常州大学 | Preparation method for hollow nano metal |
| JP2013204110A (en) * | 2012-03-29 | 2013-10-07 | Aida Kagaku Kogyo Kk | Method for producing silver fine powder and method for producing conductive paste |
| CN105127448A (en) * | 2015-09-25 | 2015-12-09 | 合肥工业大学 | Room-temperature preparation method for nano silver sheet with ultra-large area |
| CN105268988A (en) * | 2015-10-26 | 2016-01-27 | 昆明理工大学 | Method for preparing ultrafine spherical silver powder |
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- 2018-08-29 CN CN201810995204.1A patent/CN109014241B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583331A (en) * | 2004-06-10 | 2005-02-23 | 复旦大学 | Preparing method for medium hole noble metal hollow microscapsule |
| JP2013204110A (en) * | 2012-03-29 | 2013-10-07 | Aida Kagaku Kogyo Kk | Method for producing silver fine powder and method for producing conductive paste |
| CN103231069A (en) * | 2013-03-22 | 2013-08-07 | 常州大学 | Preparation method for hollow nano metal |
| CN105127448A (en) * | 2015-09-25 | 2015-12-09 | 合肥工业大学 | Room-temperature preparation method for nano silver sheet with ultra-large area |
| CN105268988A (en) * | 2015-10-26 | 2016-01-27 | 昆明理工大学 | Method for preparing ultrafine spherical silver powder |
Non-Patent Citations (1)
| Title |
|---|
| Preparation of microsized silver crystals with different morphologies by a wet-chemical method;CAI Xionghui et al.;《RARE METALS》;20100831;第29卷(第4期);第407-412页 * |
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Effective date of registration: 20220914 Address after: 230000 B-2704, wo Yuan Garden, 81 Ganquan Road, Shushan District, Hefei, Anhui. Patentee after: HEFEI LONGZHI ELECTROMECHANICAL TECHNOLOGY Co.,Ltd. Address before: No. 111, Changjiang West Road, Huaian, Jiangsu, Jiangsu Patentee before: HUAIYIN NORMAL University |